Water and wastewater treatment is a global challenge that requires innovative solutions. Electrospinning is a versatile and simple technique that allows the generation of ultrathin fibers of numerous compositions. Titanium dioxide is a photocatalyst with applications in several technological fields. Thus, the use of electrospinning to produce TiO2 nanofibers is an approach that may bring new insights for the treatment of contaminated water. In this review, it is aimed to provide a comprehensive overview of electrospinning technique and electrospun TiO2 nanofibers production, as well as their application in water and wastewater treatment. First, it is provided a brief introduction to the development of electrospinning-related processes, followed by a discussion of its principle, apparatus, methods and materials commonly used. In the sequence, it is presented the current and potential methods for electrospun TiO2 nanofibers and some aspects related to experimental conditions, catalysts immobilization, metal and nonmetal doping, characterization techniques and applications. The effects of processing parameters on properties as catalyst band gap, adsorption capacity and catalytic efficiency are also discussed. Afterward, the application of electrospun TiO2 nanofibers for pollutants removal from water through photodegradation is highlighted by focusing on some representative examples. Finally, the perspectives are presented regarding challenges, opportunities, and new directions for the application of electrospun TiO2 fibers.